Substitution products of anthanthrones



No Drawing. Application filedlfetruary 23, 1929; Serial No. 342,297,,am 1-in Germany 23,

"'. thrones by other radicals.

Patented Sept. 13, 1932 MANNHEIM, AND

MAX ALBERT KUNZ, OF

, or LUDWIGSHAFEN-O1\T-THE-RHINE, ennmnnmnss enons "we wonxs, 1110,101 NEW YORK, n. Y., A o

s s'rrimmroN rnonuors-on nnrmn'rnnonnsa The present invention relates to the production of dyestuffs and intermediate prod ucts for theipreparation of dyestuffs-ibyl'replacing the amino groups ofamino-anthan We have found that uniform which are partly: dyestuffs themselves and partly valuable intermediate products for. the preparation of dyestuffs are obtained by din azotizing the amino group orl groups of monm orpolyaminoanthanthrones. and replacing the dime group or groups by halogen -hya droxy, oarboXylic, cyano,' mercapto, thiocieno All and tetranitro derivatives are i groups, obtained group or groups.-

- The .arninoanthanthrones employed 3S1!!! tialmateria'lsaccording to our invention may be obtained by reducing; the corresponding nitro derivatives of which the mononitro compounds are obtainable according to the process. described'in the icopending application Ser. No. 341,056, filed February 18, 1929, by the action of nitric. acid on anthanthrones in a solventof highboiling point, whereas the polynitrocompound's, i. 'e. the di-, -triE- obtainable by direct nitrationof anthanthrones with strong nitric acid or a mixture of sulfuric and nitric acids, or by nitrating 1.1.-dinaphthyl-8.8- or 2.;2'-di carbox'ylic acid or derivatives there.-

of acid condensing agents. v

Valuable vat dyestuffs are obtained from anthanthrones substituted vby oxygen containing radicals, viz.;hydroXy or carboxylic in the aforesaid manner, by etherifying or esterifying the said groups. Thus, for instance,by the action of dimethylsulfate, the aliphatic or aromatic esters of p-toluenesulfonic acid, for example the methyl, ethyl, ethylene, chlorethylene, phenol and :like esters, hydroXy-anthanthrone .ethers are produced, which dissolve to green solu-' tions. in; concentrated sulfuric acid and dye cotton excellently. fast, weatherproof yellow red to red-,bluefishades from violet vats The l ofjand condensingthe products with the'a-id ever is not limited thereto. by weight;

' stirring, whereby nitrogen is PATENT ATM-LIKE 3;

KABL KOEBERLE AND onroagg'non or naaawaan Th jfi wi g xa ples furth r 1 tr" the nature of the said inve t' on which h W5 lemann" Example 1 f r 33.6 parts of dia'm'i'no anthanthronefaie dissolved in concentrated sulfuric acid and; diazoti zed in the usual mannerwith mom-- tion of N 0 in sulfuric acid or with a nitrate The solution of thefdiazo sulfateobtainedis heated at. from 90 to 100 centig'rade while;

evolvedand the initial red coloration of p the solution is changed to a greencolor'ation. After cooling, the whole is poured onto ice, and the product filteredtfi by suction" and tied. The dihydroxyanthanthrone obtained tonei, sponding to the formula; I S j tion of N' O in concentrated sulfuric ma; or witha nitrite. The diazosulfateobtained is treated either directly, or after dilution with ice, with a solution of 70 parts of potassium iodide in water while stirring. Diiodoanthanthrone of the formula:

is yformed withevolution of nitrogen. The

reaction is completed by heating to 70 centi y suction and dried. The di-iodo derivative is obtained in the form of a violet powder," which dissolves acid givinga green coloration. The purification of the'product may be carried out by crystallization from organic solvents of high boiling point of the sulfate which separates out from aqueous sulfuric acid. dyes cotton fast blue red shades from a violet vat.

--'The'corresponding dichloro or dibromoanthanthrones may be obtainedin an analogous manner 'byemploying cuprous chloride or Y cuprous bromide instead of potassium iodide.

I is a violet oration. 05 I The pure dibromo derivative obtained in this .mannergives very fast orange red shades from a red violet vat.

Example 3 powder which dissolves in concentrated sulfuric acid givinga blue'violet col- It may bepurified as described in Example 6 and may be employed as an initial grade and the reaction product is filtered off 7 in concentrated sulfuric isheated to between 80 and 90 such as nitrobenzene or by way The new dyestufi' material for the preparation of new anthanthrone derivatives.

Ewwmple 4 32 parts of monoaminoanthanthrone obtainable by reducing mononitroanthanthrone, prepared by nitrating anthanthrone in nitrobenzene, are dissolved in sulfuric acid and diazotized in the usual manner with a solution of N 0 in concentrated sulfuric acid or with a nitrite. The solution of diazosulfate obtained of the formula:

centigrade, while. stirring, whereby monohydroxyanthanthrone is formed with the evolution of nitrogen. When the coloration of the solution has changed from red violet to green the reaction is complete. After coolingand diluting the reaction mass with ice, the

monohydroxyanthanthrone is filtered off bysuction and dried and is thus obtained in the form of a red brown powder which dissolves to give a'green solution in concentrated sulfuric acid, and which dissolves in a solution of caustic alkali to give a blue green solution, and which can be precipitated from the alkaline solution in the form of violet red flakes by the addition of an; acid.

' Eaiample 5 32Qparts of the monohydroxyanthanthrone obtained accordingto the foregoing example are heatedl to boiling with 52 parts of the methyl ester or p toluene. sulfonic acid and 45 parts of potash and 30 times the amount of trichloror nitro-benzene until the formation of the dyestufl' is complete which may be recognized by the appearance of a yellow green fluorescence. The reaction mixture is best worked up by filteringthe hot solution by suction, the monomethoxyanthanthrone of the formula:

I p o separating from the filtrate in the form of a red crystalline deposit. The dyestufi obtained dissolves in concentrated sulfuric acid to give a pure green solution and recrystallizes from organic solvents having a high.

-, grade, while stirring, until nitrogen is no longer evolved and the reaction product is p then filtered off by suction and dried. The monocyanoanthanthrone o fthe formula:

is a brown yellow powder which dissolves in concentrated sulfuric acid to give a blue green solution and gives a violet red vat with alkaline hydrosulfite from which cotton is dyed yellow shades. It recrystallizes from organic solvents having a high boiling point in the form of long yellow needles. If cu- 353 prous thiocyanate be employed instead of cuprous cyanide, monothiocyanoanthanthrone of similar properties is obtained in an analogous manner. m Ewamp le '7 5 parts of the monocyanoanthanthrone obtained according to the foregoing example are heated with parts of caustic potash and 100 parts of alcohol to between 140 and 150 My degrees centigrade while stirring until a sample dissolves in a solution of caustic alkali to give a red yellow solution. The melt is taken up in water, air is passed through the solution, and the, solution is then acidified.

The anthant irone monocarboxylic acid thus 1 formed corresponding to the formula:

6G: r can be purified by dissolving it in a solution of caustic alkaliand precipitating it therefrom by means of an acid. The said carboxylic acid crystallizes from organic solvents Zhaving a high boiling point in the form of after dilution with ice by stirring. with a so-- lustrous red yellow needles sulfuric acid to give a green solution.

- The 'monocyanoanthanthrone can be transformed into the carboxylic acid equally well in an acidmedium', for example in sulfuric acid. Example 8 p 32 parts of monoaminoanthanthrone are diazotized as described in Example 8'. The diazosulphate thus obtained isconverted into monobromanthanthrone" either directly or after dilution with ice by means of a solution of 15 parts of cuprous bromidein 300 parts of hydrobromic acid. The reaction is comleted by warming to about centigrade until nitrogen is no longer evolved and the reaction productis then filtered oif by suction and dried. The monobro'ma-nthanthrone obtained corresponding to the formula:

is a brown powder which dissolves in concentrated sulfuric acid to give a green solution and gives a violet red vat with alkaline hydrosulfite from which cotton is dyed orange yellow shades. The product may be purified by recrystallization from organic solvents having a high boiling point, such as nitrobenzene, or by decomposing the sulfate which separates from aqueous sulfuric acid.

. t E ample 9 Monoaminoanthanthrone dissolved in concentrated sulfuric acid is diazotized at ordi-Z nary temperature in the, usual manner by means of a solution of nitrosyl sulfuric acid in sulfuric acid or by means of a nitrite and the.

diazosulfate solution thus obtained is converted into monoiodoanthanthrone either directly or after dilution with ice by the additionbf the calculated amount of potassium iodide dissolved in water while stirring, the said iodo-derivative separating out in the form of fine crystals. The reaction is completed by warming to about 70 centigrade while stirring and the reaction product is then filtered off b suction and dried. The monoiodoanthant rone corresponding to the formula which dissolve in:

is a brown trated sulfuric-acid to and gives a violet emon powder which dissolves in concenglve a green solution red vat with alkaline hydrosulfite from which cotton is d ed oran 'e shades. The dyestuff crystallization from a hlgh boiling may be purified by by decomposing the sulfate deposited by diluting the sulfuric acid solution of the dyestufi with water.

Example 10 32 parts of 1nonohydroxyanthantlirone obtainable according boiling, while stirring, ethyl to Example 8 are heated to with 58 parts of the ester of p-toluenesulfonic acid and 45 parts of potash in 25 times the amount of the ester employed of trich formationof the dyest may be recognized by lorobenzene, until. the uff is complete which the appearance of a yellow green fluorescence of the reaction mixture, which is then worked up as usual. The

dyestufl' obtained in the form of red crystals dissolves to a green solution in concentrated sulfuric acid and shades from a red formula:

dyes vat.

cotton very fast red It has the following Example 11 32 parts of the obtainable according to monohydroxyanthanthrone Example 8, are boiled for 5 hours, while stirring, with 60 parts of the omega-chloroethyl ester of p-toluene sulfonic acid and 45 parts the amount of benzene. as usual.

The reaction The dyestuif erties from a red vat. following formula:

of potash in 25 times the ester employed of nitromixture is worked up thus obtained is a red green solu- The dyestufl has the organic solvents having.

point such as nitrobenzen-e or in which R s v may be etheri cyano, thio-cy 2. As new tands fied or ano or articles for a hydroxy (which esterified), carboxylic, mercapto group.

of manufacture uniform derivatives of the anthanthrone series corresponding to the general formula:

o H/W in which X stands for a hydrocarbon radical which may be substituted by halogen.

3. As new articles of manufacture uniform derivatives of the anthanthrone series.

corresponding in which X stands to the general for.mu1a:

for an aliphatic hydrocarbon radical which may be substituted by halogen.

l. As a new article of manufacture the vat dyestuff corresponding to the formula forming a red crystalline powder dissolving 1 to a green solution in concentrated sulfuric What we claim is 1. As new articles of manufacture uniform derivatives of the anthanthrone series *;corresponding to the g eneral formula acid and dyeing cotton red shades.

In testimon set our hands.

from a red vat clear, y whereof we have hereunto MAX ALBERT KUNZ. KARL KOEBERLE. ERICH BERTHOLD. 

